Theoretical Study on the Noble Gas Exchange Reactions of Ng + HNBNg'(+) → Ng' + HNBNg(+) (Ng, Ng' = He, Ne, Ar, Kr, and Xe).

Abstract

High-level correlated electronic structure calculation and dual-level variational transition state theory with multidimensional tunneling calculation for rate constants have been performed on four noble gas exchange reactions [(1) He + HNBHe'(+) → He' + HNBHe(+), (2) He + HNBNe(+) → Ne + HNBHe(+), (3) Ne + HNBNe'(+) → Ne' + HNBNe(+), and (4) Ar + HNBAr'(+) → Ar' + HNBAr(+)] and on three (3)He isotopic analogues (He + HNB(3)He(+), (3)He + HNBHe(+), and (3)He + HNB(3)He(+)) of the first reaction. The classical barrier heights were predicted to be 8.9, 6.8, 5.7, and 5.5 kcal/mol for the four reactions, respectively. The tunneling effects were found to be important below 250 K for the He reactions and below 150 K for the Ne and Ar reactions. Kinetic helium isotope effects as large as 7.8 at 100 K were predicted for the (3)He + HNB(3)He(+) reaction. Additionally, the structures and energies of the Kr + HNBKr'(+) and Xe + HNBXe'(+) systems have also been studied.